EP1367059B1 - Organosiliciumverbindungen, Verfahren zu ihrer Herstellung und ihre Verwendung - Google Patents

Organosiliciumverbindungen, Verfahren zu ihrer Herstellung und ihre Verwendung Download PDF

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Publication number
EP1367059B1
EP1367059B1 EP03009379A EP03009379A EP1367059B1 EP 1367059 B1 EP1367059 B1 EP 1367059B1 EP 03009379 A EP03009379 A EP 03009379A EP 03009379 A EP03009379 A EP 03009379A EP 1367059 B1 EP1367059 B1 EP 1367059B1
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EP
European Patent Office
Prior art keywords
mixtures
organosilicon compounds
rubber
compounds according
mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP03009379A
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German (de)
English (en)
French (fr)
Other versions
EP1367059A2 (de
EP1367059A3 (de
Inventor
Roland Dr. Krafczyk
Ulrich Dr. Deschler
Hans-Detlef Dr. Luginsland
Pieter Dr. Reimund
Andre Hasse
Melanie Mayer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
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Filing date
Publication date
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Publication of EP1367059A3 publication Critical patent/EP1367059A3/de
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Publication of EP1367059B1 publication Critical patent/EP1367059B1/de
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/548—Silicon-containing compounds containing sulfur
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S152/00—Resilient tires and wheels
    • Y10S152/905—Tread composition

Definitions

  • the invention relates to mixtures of organosilicon compounds, a Process for their preparation and their use.
  • silanes As adhesion promoters.
  • aminoalkyltrialkoxysilanes, methacryloxyalkyltrialkoxysilanes, polyoulfanalkyltrialkoxysilanes and mercaptoalkyltrialkoxysilanes are used as adhesion promoters between inorganic materials and organic polymers, as crosslinking agents and surface modifiers (EP Plueddemann, "Silane Coupling Agents", 2 nd Ed., Plenum Press 1982).
  • adhesion promoters or coupling orilorsageniien form both the filler as also to the elastomer bonds and thus effect between the filler surface and the elastomer one good interaction.
  • a disadvantage of the known mercaptosilanes according to DE 10015309 is the necessary addition of alkylsilanes too Rubber blends to certain properties receive.
  • methoxy and ethoxy substituted Silanes are more reactive than that corresponding long-chain alkoxy-substituted Silane and thus faster change the filler can, so that on the use of methoxy and ethoxy substituents from technical and economic View can not be waived
  • R is a methyl or ethyl group
  • R ' are identical or different and is a C 9 -C 30 branched or unbranched monovalent alkyl or alkenyl group, aryl group, aralkyl group, branched or unbranched C 2 -C 30 alkyl ether group, branched or unbranched C 2 -C 30 alkyl polyether group
  • the object of the invention is to provide a To provide organosilicon compound, with the good hardness and dynamic in rubber compounds Stiffness can be achieved.
  • Another object of the invention is to provide a To provide organosilicon compound, with in rubber mixtures even without the addition of Alkyl silanes comparable properties to those in DE 10015309 can be achieved.
  • the invention relates to mixtures of organosilicon compounds of the general formula I and / or II where R is a methyl or ethyl group, R 1 is the same or different and is a C 9 -C 30 branched or unbranched monovalent alkyl group, R 2 is a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic / aromatic C 1 -C 30 hydrocarbyl group, which are characterized in that the mixture contains different components with different R 'groups and the proportion of one component of the mixture is 10 to 50 mol%, preferably 10 to 40 mol%, particularly preferably 15 to 30 mol%.
  • R 1 may for example consist of 10 to 50 mol% of C 14 H 29 and 90 to 50 mol% of C 12 H 25 or of 10 to 50 mol% of C 18 H 37 and 90 to 50 mol% of C 16 H 33 , R 1 can also consist of more than two different R 1 .
  • R 2 can be CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 , CH (CH 3 ), CH 2 CH (CH 3 ), C (CH 3 ) 2 , CH ( C 2 H 5 ), CH 2 CH 2 CH (CH 3 ), CH 2 CH (CH 3 ) CH 2 or mean.
  • Another object of the invention is a process for preparing mixtures of organosilicon compounds of the general formula I and / or II, which is characterized in that silanes of the general formula III in which R and R 2 have the abovementioned meaning, with mixtures of alcohols of the general formula R 1 -OH, in which R 1 has the abovementioned meaning and is used as a mixture of at least two alcohols (R 1 is different), with cleavage of R-OH, and R-OH is separated by distillation continuously from the reaction mixture.
  • alcohol mixtures of 10 to 50 mol% C 14 H 29 OH and 90 to 50 mol% C 12 H 25 OH or alcohol mixtures of 10 to 50 mol% C 18 H 37 OH and 90 to 50 mol% C 16 H 33 OH are used. It is also possible to use alcohol mixtures with several components (R 1 ).
  • alcohol mixtures R 1 -OH for example Lorol Spezial or Stenol 1618 (cetyl / stearyl alcohol) of the manufacturer Cognis or Ecorol 68/50 (cetylstearyl alcohol) of the manufacturer Ecogreen Oleochemicals can be used.
  • a mixture can be formed in which none, one, two or three of the RO groups are replaced by R 1 O groups.
  • the ratio of the RO to R 1 O groups can be determined by the molar ratio of the silane of the general formula III to the alcohol of the formula R 1 -OH.
  • a mixture of organosilicon compounds having an average composition according to the formula I can be obtained.
  • a mixture of organosilicon compounds having an average composition according to the formula II can be prepared.
  • the reaction can be neutral, acid or basic catalysts, such as hydrochloric acid, Sulfuric acid, phosphoric acid, formic acid, acetic acid, para-toluenesulfonic acid, sodium hydroxide solution, potassium hydroxide solution, Sodium methylate, sodium ethylate, ion exchange resins Amberlyst 15, Deloxan ASP I / 9 or metal compounds, in particular titanates, for example known from US 2820806, accelerate.
  • acid or basic catalysts such as hydrochloric acid, Sulfuric acid, phosphoric acid, formic acid, acetic acid, para-toluenesulfonic acid, sodium hydroxide solution, potassium hydroxide solution, Sodium methylate, sodium ethylate, ion exchange resins Amberlyst 15, Deloxan ASP I / 9 or metal compounds, in particular titanates, for example known from US 2820806, accelerate.
  • the reaction can be carried out at temperatures between 20 and 200 ° C, preferably between 20 and 150 ° C, carry out. To avoid condensation reactions It may be beneficial to have the reaction in one anhydrous, ideally in an inert gas atmosphere, perform.
  • the mixtures of organosilicon compounds according to the invention can as a bonding agent between inorganic materials (For example, glass fibers, metals, oxidic Fillers, silicas) and organic polymers (for example, thermosets, thermoplastics, elastomers) or as crosslinking agents and Surface modifiers are used.
  • inorganic materials For example, glass fibers, metals, oxidic Fillers, silicas
  • organic polymers for example, thermosets, thermoplastics, elastomers
  • crosslinking agents and Surface modifiers are used.
  • the Mixtures of organosilicon compounds according to the invention can be used as Primer in with silica and / or starch filled tires are used.
  • Rubber mixtures which thereby gekennt university are that they are rubber, filler, such as precipitated silica, optionally further Rubber auxiliary, as well as at least one Inventive mixture of organosilicon compounds.
  • the mixtures of organosilicon compounds according to the invention can be described in Amounts of 0.1 to 20% by weight, based on the amount of used rubbers are used.
  • the addition of the mixtures according to the invention of Organosilicon compounds, as well as the addition of Fillers may preferably be at melt temperatures of 100 up to 200 ° C take place. However, she can also join later lower temperatures (40 to 100 ° C), for example carried out together with other rubber auxiliaries
  • the mixtures of organosilicon compounds can be both in pure form as well as reared on an inert organic or inorganic carriers are added to the mixing process.
  • Preferred support materials are silicic acids, waxes, Thermoplastics, natural or synthetic silicates, Alumina or carbon blacks.
  • the fillers mentioned can be used alone or in a mixture be used.
  • the rubber vulcanizates according to the invention can contain other rubber adjuvants, such as Reaction accelerator, anti-aging agent, Heat stabilizers, light stabilizers, Antiozonants, processing aids, Plasticizers, tackifiers, blowing agents, dyes, Pigments, waxes, extenders, organic acids, Retarders, metal oxides and activators, such as Triethanolamine, polyethylene glycol, hexanetriol, which is the Rubber industry are known.
  • Rubber adjuvants such as Reaction accelerator, anti-aging agent, Heat stabilizers, light stabilizers, Antiozonants, processing aids, Plasticizers, tackifiers, blowing agents, dyes, Pigments, waxes, extenders, organic acids, Retarders, metal oxides and activators, such as Triethanolamine, polyethylene glycol, hexanetriol, which is the Rubber industry are known.
  • the rubber auxiliaries may be used in known quantities, among other things according to the purpose be used. Usual amounts are for Example amounts of 0.1 to 50 wt .-%, based on Rubber. As crosslinkers, sulfur or Sulfur-donating substances are used.
  • the Rubber mixtures according to the invention can be used over it also contain vulcanization accelerators. Examples for suitable main accelerators Mercaptobenzothiazoles, sulfenamides, thiurams, Dithiocarbamates, more preferably sulfenamides, in Amounts of 0.5 to 3 wt .-%. Examples for Coban accelerators are guanidines, thioureas and Thiocarbonates in amounts of 0.5 to 5 wt .-%. sulfur can usually be used in amounts of from 0.1 to 10% by weight, preferably 1 to 3% by weight, based on rubber, be used.
  • Rubber compounds can be used at temperatures of 100 to 200 ° C, preferably 130 to 180 ° C, optionally under Pressure of 10 to 200 bar done.
  • the mix of Rubbers with the filler, if necessary Rubber auxiliaries and the mixture of Organosilicon compounds may be known in the art Mixing units, such as rollers, internal mixers and Mixing extruders are performed.
  • the rubber mixtures according to the invention are suitable for the production of moldings, for example for the Production of pneumatic tires, tire treads, Cable sheaths, hoses, transmission belts, conveyor belts, Roll coverings, tires, soles, sealing rings and Damping elements.
  • mixtures of organosilicon compounds according to the invention can be used together with high surface area silicas having CTAB 180-220 m 2 / g in rubber mixtures, in particular in truck running surfaces.
  • the rubber mixture according to the invention can for the Manufacture of tire treads with improved lower rolling resistance, improved Wet skid resistance and consistently good Dry properties compared to a same Rubber mixture, wherein the mixtures of the invention of Organosilicon compounds in a molar ratio on the silicon units from 1: 1.8 to 1: 2.7 against Exchanged bis (3-triethoxysilylpropyl) tetrasulfide is to be used.
  • the rubber mixture according to the invention can for the Manufacture of tire treads with improved lower rolling resistance and an improved Wet skid resistance with consistently good Abrasion resistance to a same Rubber mixture, wherein the mixtures of the invention of Organosilicon compounds in a molar ratio on the silicon units from 1: 1.8 to 1: 2.7 against Exchanged bis (3-triethoxysilylpropyl) tetrasulfide is to be used.
  • the mixtures of organosilicon compounds according to the invention have the advantage over organosilicon compounds according to EP 1 285 926 that the hardness and the dynamic Stiffness E * is increased at constant tan ⁇ 60 ° C (correlated with rolling resistance).
  • the mixtures of organosilicon compounds according to the invention have the advantage that less methanol or Ethanol is released than in the known silanes, with constant reactivity.
  • the non-volatile Alcohols are not due to their inactivity separated or remain of the organosilicon compound due to their non-volatility in the polymer matrix. In both cases they are not released into the environment.
  • the mixtures according to the invention of Organosilicon compounds have the advantage that on the Addition of alkylsilane according to DE 10015309 omitted can be, as in the inventive mixtures of Organosilicon compounds of the formula I and / or II, a deterioration of processability, as in Trap of, for example, 3-mercaptopropyltrimethoxy or 3-mercaptopropyltriethoxysilane, not found.
  • the rubber mixtures according to the invention have the Advantage over bis (3-triethoxysilylpropyl) tetrasulfide containing rubber mixtures that the Dynamic stiffness is lowered and thus are particularly suitable for winter tires (soft Mixture).
  • the recipe used for the rubber compounds is given in Table 1 below.
  • the unit phr means parts by weight, based on 100 parts of the raw rubber used.
  • the mixtures of organosilicon compounds according to the invention are metered equimolar to 3-mercaptopropyltriethoxysilane, based on silicon.
  • the general process for preparing rubber mixtures and their vulcanizates is described in the book: "Rubber Technology Handbook", W. Hofmann, Hanser Verlag 1994.
  • the polymer VSL 5025-1 is an in Solution polymerized SBR copolymer of Bayer AG with a styrene content of 25 wt .-% and a Butadiene content of 75 wt .-%.
  • the copolymer contains 37.5 phr of oil and has a Mooney Viscosity (ML 1 + 4/100 ° C) of 50 ⁇ 4.
  • the polymer Buna CB 24 is a cis 1,4-polybutadiene (neodymium type) from Bayer AG with cis 1,4 content of at least 97% and a Mooney viscosity from 44 ⁇ 5.
  • Vulkanox 4020 is 6PPD Bayer AG and Protektor G35P is an ozone protection wax the HB-Fuller GmbH.
  • Vulkacit D (DPG) and Vulkazit CZ (CBS) are commercial products of Bayer AG.
  • Ultrasil 7000 GR is a readily dispersible precipitated silica from Degussa AG with a BET surface area of 170 m 2 / g.
  • 3-mercaptopropyltriethoxysilane is manufactured by ABCR GmbH CoKG and VP Si 208, octyltriethoxysilane, is a commercial product of Degussa AG.
  • the rubber mixtures are prepared in an internal mixer according to the mixing instructions in Table 2.
  • step 1 settings mixing unit Werner & Pfleiderer E type rotation speed 70 min -1 stamp printing 5.5 bar void 1,58 l filling level 0.56
  • Flow temp 80 ° C mixing process 0 to 1 min Buna VSL 5025-1 + Buna CB 24 1 to 3 min 1/2 filler, ZnO, stearic acid, naftols ZD, organosilicon compounds 3 to 4 min 1/2 filler, aging protection 4 min Clean 4 to 5 min Mix, 5 min Clean 5 to 6 min Mix and extend Batch temp.
  • Table 3 summarizes the rubber testing methods. Physical testing Standard / Conditions ML 1 + 4, 100 ° C, 3rd stage DIN 53523/3, ISO 667 Vulcameter test, 165 ° C t10% and t90% (min) DIN 53529/3, ISO6502 Tensile test on the ring, 23 ° C DIN 53504, ISO 37 Tensile strength (MPa) Voltage values (MPa) Elongation at break (%) Shore A hardness, 23 ° C (SH) DIN 53 505 Viscoelastic properties, 0 and 60 ° C, 16 Hz, 50 N pre-load and 25 N amplitude force Dynamic module E * (MPa) Loss factor tan ⁇ () DIN 53 513, ISO2856 Ball Rebound, 60 ° C (%) ASTM D 5308 Goodrich Flexometer DIN 53 533, 0.25inch stroke, 25 min., 23 ° C Contact temperature (° C) Penetration temperature (° C) Permanent Set (%) ASTM D 623 A DIN abrasion, 10 N
  • Table 4 shows the results of the rubber technical examination.
  • the mixtures are vulcanized at 165 ° C for 20 minutes.
  • Rohmischungsease 1 2 3 characteristics unit ML (1 + 4) at 100 ° C, 3rd stage [MU] 69 62 72 MDR, 165 ° C, 0.5 ° t 10% [Min] 0.8 1.0 0.8 t 90% [Min] 5.9 15.6 16.8 Vulkanisatdetecting
  • the recipe used for the rubber compounds is given in Table 5 below.
  • the mixture of silanes according to the invention is metered equimolar to Si 69 based on silicon.
  • the sulfur adaptation is necessary to compensate for the lower sulfur content of the mixtures of organosilicon compounds according to the invention.
  • masterbatch A B rubber blend S-SBR / BR / NR 100 100 Highly dispersible silica 80 80 soot 6.6 6.6 Aromatic plasticizer 30 24 Si 69 6.6 --- Mixture of organosilicon compounds according to Ex. 3 --- 5.95 chemicals ready-mix A B Ground sulfur 2.0 2.8 accelerator mixture
  • the rubber compounds are four-stage in one Internal mixer made. All components of the Basic mixture are mixed in the first mixing stage, followed by two Zwickton and a final stage in the the accelerators and the sulfur are added.
  • the mixing temperatures of the first three mixing stages are in the range of 140-160 ° C and the temperature of fourth stage ⁇ 120 ° C.
  • Table 6 summarizes the methods for rubber testing.
  • Tensile test on the ring 23 ° C
  • Table 7 shows the results of the rubber testing.
  • the mixtures are vulcanized at 165 ° C for 10 minutes.
  • the two tread compounds A and B are used to build the test tires A and B, size 205 / 65R15 94V and tested by Smithers Scientific Services Inc.
  • Table 8 shows the test types and test conditions used.
  • the road tests are driven by a BMW 528i.
  • the required tire pressure is 2.1 bar, the rear tire pressure 2.5 bar.
  • the payload in front is 903 kg, rear 911 kg.
  • the relative rating of the test tire B with the blend B of the invention relative to the reference tire A is shown in Table 9. Values greater than 100 mean an improvement.
  • FIG. 1 shows the curved path.
  • FIG. 1 shows the curved path.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP03009379A 2002-05-28 2003-04-25 Organosiliciumverbindungen, Verfahren zu ihrer Herstellung und ihre Verwendung Expired - Lifetime EP1367059B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10223658 2002-05-28
DE10223658A DE10223658A1 (de) 2002-05-28 2002-05-28 Organosiliciumverbindungen, Verfahren zu ihrer Herstellung und ihre Verwendung

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EP1367059A2 EP1367059A2 (de) 2003-12-03
EP1367059A3 EP1367059A3 (de) 2003-12-10
EP1367059B1 true EP1367059B1 (de) 2005-02-02

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US (2) US20030229166A1 (ja)
EP (1) EP1367059B1 (ja)
JP (1) JP4426212B2 (ja)
KR (1) KR100972302B1 (ja)
AT (1) ATE288440T1 (ja)
DE (2) DE10223658A1 (ja)
ES (1) ES2233893T3 (ja)
PL (1) PL209209B1 (ja)

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KR102029759B1 (ko) 2012-04-05 2019-10-08 에보니크 데구사 게엠베하 메르캅토실란-카본 블랙 블렌드

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DE102004061014A1 (de) * 2004-12-18 2006-06-29 Degussa Ag Kautschukmischungen
DE102005057801A1 (de) 2005-01-20 2006-08-03 Degussa Ag Mercaptosilane
DE102005020535B3 (de) * 2005-05-03 2006-06-08 Degussa Ag Verfahren zur Herstellung von Mercaptoorganyl(alkoxysilanen)
DE102005038791A1 (de) * 2005-08-17 2007-02-22 Degussa Ag Organosiliciumverbindungen, ihre Herstellung und ihre Verwendung
DE102005043202A1 (de) 2005-09-09 2007-03-15 Degussa Ag Fällungskieselsäuren mit besonderer Porengrößenverteilung
DE102005043201A1 (de) 2005-09-09 2007-03-15 Degussa Ag Fällungskieselsäuren mit einer besonderen Porengrößenverteilung
JP5520483B2 (ja) * 2005-09-21 2014-06-11 チバ ホールディング インコーポレーテッド 改善された加工性を有する充填ゴム配合物
DE102005060122A1 (de) * 2005-12-16 2007-06-21 Degussa Gmbh Verfahren zur Herstellung von (Mercaptoorganyl)alkylpolyethersilanen
DE102006004062A1 (de) * 2006-01-28 2007-08-09 Degussa Gmbh Kautschukmischungen
DE102006027235A1 (de) * 2006-06-09 2008-01-17 Evonik Degussa Gmbh Kautschukmischungen
DE102006033310A1 (de) * 2006-07-17 2008-01-31 Evonik Degussa Gmbh Gemische aus siliciumhaltigen Kopplungsreagentien
EP1978024A1 (en) * 2007-04-04 2008-10-08 Atotech Deutschland Gmbh Silane compositions comprising novel crosslinking agents
JP5319108B2 (ja) * 2007-12-25 2013-10-16 株式会社ブリヂストン ゴム組成物及びそれを用いたタイヤ
DE102008017747A1 (de) 2008-04-07 2009-10-08 Evonik Degussa Gmbh Gefällte Kieselsäuren als Verstärkerfüllstoff für Elastomermischungen
KR200451724Y1 (ko) * 2008-10-06 2011-01-07 주식회사 뉴빛 스타일러스 펜이 구비된 모바일기기용 액세서리
DE102010017805A1 (de) * 2010-07-08 2012-01-12 Continental Reifen Deutschland Gmbh Kautschukmischung
DE102015224450A1 (de) * 2015-12-07 2017-06-08 Evonik Degussa Gmbh Kautschukmischungen
DE102017221259A1 (de) 2017-11-28 2019-05-29 Evonik Degussa Gmbh Silanmischungen und Verfahren zu deren Herstellung
EP4023460A1 (en) * 2020-12-30 2022-07-06 The Goodyear Tire & Rubber Company Sulfur curable rubber formulation, tire component and silica

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EP1367059A2 (de) 2003-12-03
ATE288440T1 (de) 2005-02-15
US20060241224A1 (en) 2006-10-26
ES2233893T3 (es) 2005-06-16
US7767742B2 (en) 2010-08-03
DE10223658A1 (de) 2003-12-18
PL360360A1 (en) 2003-12-01
JP4426212B2 (ja) 2010-03-03
DE50300291D1 (de) 2005-03-10
PL209209B1 (pl) 2011-08-31
EP1367059A3 (de) 2003-12-10
US20030229166A1 (en) 2003-12-11
KR20030091825A (ko) 2003-12-03
JP2004002428A (ja) 2004-01-08
KR100972302B1 (ko) 2010-07-26

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